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Vol. 67
COMMUNICATIONS TO THE EDITOR
The final product was obtained in two fractions: mm.), n2% (a) The first distils at 100-103° 1.5640,showing an absorption maximum a t 312 m r and a molecular coefficient of extinction of 27,450. Anal. Calcd. for C21Ha20: C, 83.94; H, 10.74. Found: C, 83.74; H, 10.59. (b) The second distils a t 110-115° (10-3mm.), n26D 1.5771, showing an absorption maximum a t 315 m r and a molecular coefficient of extinction of 33,750. Anal. Calcd. for C21H32O: C, 83.94; H, 10.73. Found: C, 83.79; H, 10.69. Figure 1 shows the similarity in shape of the absorption curves o! products V to that of Vitamin A alcohol. The slight displacement of the maxima and the lower maximum intensities of absorption may indicate stereoisomeric variations from the natural product. Biological assays are a t present in progress.
50t
A
methods in which the acetoxy analog of 118 is condensed with I. I n addition to the magnesium derivative of I, the zinc derivative is being investigated in view of its inertness toward esters. ORTHO RESEARCH FOUNDATION ORGANIC CHEMISTRY DIVISIO?~ LINDEN,NEWJERSEY 'WILLIAM OROSHNIK RECEIVED AUGUST17, 1945 REACTIONS OF VANILLIN
Sir: In a search for a simple process for converting vanillin directly into vanillic acid, it was found that silver oxide and excess alkali in aqueous solution effected this transformation. Unlike other alkaline silver oxide oxidations of aldehydes which require one mole of oxide to one mole of aldehyde, this oxidation took place with only one-half mole of silver oxide according to the equation 2 RCHO
+ Ag,O + 2 NaOH
NaOH
2 RCOONa
+ 2 Ag + &O + HI
This unexpected discovery led to the assumption of a Cannizzaro mechanism for the reaction and ' 3 0 this hypothesis was confirmed by experiments 2 employing less than one-ha'. mole of silver oxide x in which vanillyl alcohol (ir the form of its dimer) 20 was recovered in the calculated amount, depending upon the amount of silver oxide used. Thus, a mixture of 1.0 mole of vanillin, 0.25 mole of 10 freshly prepared silver oxide, 4.0 moles of sodium 1 hydroxide and 1000 g. of water was heated to I boiling for one hour and filtered. Acidification 250 300 350 of the filtrate with carbon dioxide yielded 34.2 g. m. (corresponding to 0.24 mole of vanillyl alcohol) Fig. 1.-Curve 1, vitamin A, alcohol; curve 2, product V 4,4'-dihydroxy - 3,3'- dimethoxydiphenylmethane, m. p. 108-109O (from water or ligroin) (Anal. (b); curve 3 , Froduct I' (a); solvent, isopropanol. Calcd. for ClsHleOa: C, 69.20; H, 6.20; CHa0, When the crude acetylenic compound I114 was 23.85. Found: C,68.99;H, 6.23; CH30, 23.69). hydrogenated in the presence of a poisoned pal- The carbonated filtrate yielded 119.6 g. (0.71 ladium catalyst only the theoretical quantity of mole) of vanillic acid, m. p. 209-210'. It was hydrogen for the semihydrogenation of one acetyl- further found that the active silver metal proenic bond was absorbed. The resulting divinyl duced in the above reaction would catalyze a carbinol, IV, distilled a t 113-115' mm.), Cannizzaro reaction of vanillin to give equivalent n2% 1.5099 and, as would be expected theo- amounts of vanillic acid and polymerized vanillyl retically, showed no significant absorption in the alcohol. I n the presence of alkali alone vanillin ultraviolet. does not undergo a Cannizzaro A d . Calcd. for C21HU02: C, 79.19; H, 10.76. In addition to vanillin, other ortho- and paraFound: C, 79.37; H, 10.63. The yield of IV hydroxy- and amino-substituted benzaldehydes, from I was 84%. ordinarily inert in the presence of strong alkali, The rearrangement and simultaneous dehydra- easily underwent the Cannizzaro reaction in the tion of the divinyl carbinol IV to products V (a) presence of active silver to yield the derived acid and V (b) was accomplished in glacial acetic acid and unpolymerized alcohol. Active silver also with a trace of #-toluenesulfonic acid at room catalyzed the crossed Cannizzaro reaction of these temperature. Thk total yield of (a) and (b) from aldehydes with formaldehyde to give substantially IV was 7770, quantitative yields of unpolymerized alcohols, Work is.at present in progress toward the syn- even in the case of vanillin. thesis of the corresponding acetate of V by similar *?
(4) The crude acetylenic compound 111 split out water spontaneously on distillation a t 10-a mm., and the redistilled product hoiled at 112-114' ( l o - ' mm.), l t * @ ~1.5715. A n d . Calcd. for ( ' , ~ H n 1 0 . C . R4.51: H . 10.13. Found: C . 84.10: H. 10.28.
(1) Lock, D e r , 62, 1181 (1929) (2) Raikow and Raschtanow Oeslerr Chcm ZLg 6, 1G9 (1902)
(3) Tomlinson and Hibbert, THISJOURNAL, I S , 349 (1936) (4) Geissman. Chapter 2 in Adams, "Organic Reactions," Vol I 1 John Wiley and S o n 4 Inc N P WYork. N Y 1944 p 104-107
NEW BOOKS
Sept., 1945
Oxidations of vanillin have also been obtained with mercuric and auric oxides but, in these cases, the Cannizzaro reaction was inoperative. The experimental details and theoretical con-
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siderations of these investigations will appear in a forthcoming series of papers. T~~ I~~~~~~~~ OF pAPER cHEMISTRY
APPLETON, WISCONSIN IRWISA. PEARL RECEIVED Auc:usr 17. 1915
NEW BOOKS Physico-Chemical Methods. By JOSEPH REILLY,Boyle Medallist, Royal Dublin Society, Professor of Chemistry, University College, Cork, and William Norman Rae, Professor of Chemistry and Physics, Royal College of Surgeons in Ireland. Volume I and Volume 11. Fourth edition. D. Van Nostrand Company, Inc., 250 Fourth Avenue, New York, N. Y.,1944. Volume I: ix 4-610 pp. Volume 11: vii 585 pp. Illustrated. 16 X 24.5 cm. Price, $17.50. According to the authors, “No drastic alterations have been made in the present edition.” Nevertheless considerable new material has been added to the comprehensive treatment of the previous edition. Some twentyfive new pages deal with-surface area, thermopiles, the tensile strength of liquids, microfractionation, micro diffusion, the ultracentrifuge and artificial radioactivity. There are numerous other interesting additions of less significance. The purpose of the authors, as stated in the first edition, is to describe laboratory procedures a t a much more advanced level than is possible in a manual for undergraduate students and thus make it unnecessary for an investigator to go to sources which are often not readily accessible. This objective has been only partially realized. While it is possible in the case of many procedures to give complete instructions, more complicated apparatus, such as the ultracentrifuge, can only be properly constructed by reference to the original literature. In the discussion of these topics the work becomes more of a commentary, with references, than a laboratory directive. As such it will serve as a convenient starting point for one beginning a search of the literature. Apparently most of the fourth edition is printed from the plates of the third edition. New materials have been introduced by the expedient of eliminating cuts in some places and using a decimal system of paging (i. e., 18.1, 18.3,etc.) in other places. Chapter XI11 has been omitted entirely for no obvious reason. This chapter entitled “Molecular Propcrties” in the third edition included the sub-titles of solubility, molecular weights, molecular weights-micro methods, partition coefficients, rates of reaction. mass action and stability of explosives. The paper and binding are not up to the excellent standard of the third edition. While apparently less durable they are probably satisfactory except for the hardcqt usage. H. E. BENT
interested in the serum proteins in general, or their ultracentrifugal behavior in particular, is contained in this volume. The outstanding contributions reported here are uiidoubtedly his elucidation of the behavior of the so-called “X-protein” of human serum or plasma, first described by McFarlane in 1935, and the description of a new serum globulin of low molecular weight (ca. 50,000) called “fetuin.” The X-protein of human serum is found to have a sedimentation behavior in the ultracentrifuge highly dependent upon the density of the centrifuged solution. From studies of the dependence of sedimentation constant upon density, the specific volume of this component is calculated to be 0.969, a value remarkably large for a protein molecule. Certain serum fractions prepared by high-speed centrifugation or electrophoresis are shown to have sedimentation properties similar to those of this labile component of human serum. These fractions were found to be rich in /3-globulin and lipid. Pedersen says that to date he has observed no components showing this “density effect” in sera other than human. The low molecular weight globulin fetuin Jvas first observed in serum from newly born calves. It has also been found in large quantities in the serum from the foal and from sheep foetus. Pedersen points out that these cases where fetuin is found represent animals where the antibodies do not appear in the serum of the newborn until it has received colostrum, whereas in rodents and man the antibodies are known to be transferred from the mother to the foetus. A large part of this thesis describes ultracentrifuge studies of various fractions of serum obtained by animonium sulfate precipitation, and of various “delipidated” sera. These experiments were made with the serum or plasma of the adult cow, calf, calf foetus, adult and foetal rabbit, foal, sheep foetus, normal adult human, pathological adult human, and human umbilical cord. This very ambitious program is well described in a series of about forty tables. Unfortunately, there is not much supplementary chemical or electrophoretic work upon these fractiotis, but this deficiency is very understandable when it is remembered that this large mass of data was obtained i i i connection with experiments primarily concerned with ultracentrifugal studies. Some of the other conclusions of the author are of considerable interest. Observations concerning the isohetnagglutinins of human serum are presented, but unfortunately there are few data presented in the form of quantitative immunological assay of the materials used. Several yUltracentrifugal Studies on Serum and Serum Fractions. globulin fractions were prepared and studied, and gave By KAI 0. PEDERSEN.To be obtained through Alm- molecular weights from 153,000 for human y-globulin, to quirt and Wiksetls AB, lipsala, Sweden, 1945. 178 pp. 192,000 for a yglobulin fraction from cow serum. Serum 10 5 X 24 cm. Price, 10 Swedish crowns (about $2.50). albumin from hutnan and from cow foetus serum were also Thi.i thesis of Pedersen’s has been long awaited by all rather intensively investigated, as were several high who hid seen preliminary reports of his work on the serum molecular weight globulins obtained from pathological proteins in “The Ultracentrifuge” by Svedberg and human serum. This valuable cnntrihutinn to protein arid ultrarentriPe.tler.;en. A grrat deal of valuable information for anyone
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